Manufacture of vat dyestuffs



Patented Jan. 19, 1932 UNITED-STATES P AT E N T F ICE MAX ALBERT KUNZ,OF MANNHEIM, AND KARL KOBERLE, OF LUDwlGsflAiEN ONl-TfiEy- RHIN'E,GERMANY, ASSIGNORS T0 GENERAL ANILINE WORKS, INC, OF NE-W'. YORK N. Y.,A CORPORATION OF DELAWARE MANUFACTURE OF VAT DYESTUFFS No Drawing.Application filed June 16, 1927, Serial No. 199,420, and in Germany June30, 1926.

It is well known that ms-benzdianthrone, when treated with aluminiumchlorid, furnishes ms-naphthodianthrone of the formula 2 atoms ofhydrogen being splitolf. 2.2-dimethyl-ms benzdianthrone behaves in anentirely analogous manner. From the tinctorial point ofvlew, thenis-naptho-dianthrones possess even less lnterest than the ms-benzdl- Ianthrones, since it is only after an addition densation products,entirely different from those already mentionedcan be obtained withexcellent yields by subjecting 2.2-dimethylms-benzianthrone or itsderivatives to the inv fiuence of'agents with an alkaline reaction,

preferably alkaline condensing agents, for example calcined sodiumcarbonate, sodium acetate, potassium carbonate, barium oxid,

caustic potash, alcoholic caustic potash, and the like, if desired inthe presence of solvents or diluents. It is probablethat, under theseconditions, a condensation takes place with the formation of a newhexagon ring with the aid of the two methyl groups, in accordance. Withthe following formulae:

The new products, which we have termed allo-ms-naphthodianthrones,V areexcellent vat dyestufis, and, in addition, form. Valuable initialmaterials for the production of other dyestuffs, by reason of theirgreat reactivity.

New and particularly Valuable vat dyestuffs can be obtained by treatingthe afore-- said allo-ms-naphthodianthrones with acid" condensingagents, such as aluminium chlorid, and the like, with or without thepresence of-solvents. The same new dyestufl's are also formed bysubjecting the said originali dyestuffs, the allo-ms-naphthodianthrones,dissolved in concentrated sulfuric acid, to the action of light or ofoxidizingagents such as: lead dioxid, manganese dioxid, nitric acid, andthe like. It is probable that by such treatments further condensationiseffected with additional ring formation according to the formulae:

The new products may be termed ms-anthradianthrones. They generallydissolve in concentrated sulfuric acid to a violet to blue solution, andthe bluish-violet vats give dyebags, on cotton, of similar shades which,when washed and soaped, change to a golden yellow extremely fast tolight and chlorine.

The same ms-anthradianthrones are produced when2.2-dimethyl-ms-naphthodianthrone or its derivatives are treated withalkaline agents in the manner already described with reference to the2.2-dimethylms-benzdianthrones. In this reaction probably 4 atoms ofhydrogen are split off, thereby leading to the ring system ofins-anthradianthrone, as in the following formulae:

on. my? 0;? l l fiu 0 o 8 ll 2.241methyl-ms-napthoms-anthradianthrone.

dhnthrone dyestuffs.

once or absence of catalysts.

The introduction of halogen may be offected in various ways. Forexample. halogen, or agents liberating the same, may be allowed to acton the dyestuffs in the pres- Suitable catalysts for this purpose, arefor example, iodine, sulfur metals and metallic salts. The reaction ispreferably carried on in solvents or diluents. Other methods, however,may be adopted. For instance, in the case of the ins-anfhradianthrones,the halogen-allo-msnaphthodianthrones, obtainable by halogenating theallo-ms-naphthodianthrones un er the conditions above specified, may betrans formed, by treatment with acid condensing agents, or by the actionof oxidizing agents or light in acid solution, into the correspondinghalogen-ms-anthradianthrones. ()n the other hand, theallo-ms-naphthodianthrones obtainable by the action of alkaline agentson 2.2'-dimethyl-ms-benzdianthrone or its derivatives, may be subjectedto treatment with halogen and simultaneous condensation, for example totreatment with halogen under pressure, whereby halogenation andcondensation are effected simultaneously.

' By the above mentioned methods of halogenation alsohalogen-ms-naphthodianthrones can be obtained from ms-naphthodianthroneor its derivati 'es. The same halogenated ms naphthodianthrones are alsoobtainable by subjecting halogenated ms-benzdianthrones to condensationin the aforesaid manner or not halogenated msbenzdianthrones tosimultaneous condensation and halogenation. The halogenatedmsnaphthodianthrones thus obtainable are of comparatively low "alue asvat dyestuffs, but are valuable intermediary products for the productionof other vat dyestuffs.

For purification, the afore-described halogenated dyestuffs may berecrystallized from solvents of high boiling point. or may he treated,in paste form, with hypochlorite. They usually give blue toreddish-violet solutions in concentrated sulfuric acid in some caseswith more or less strong fluorescence, and furnish, with an alkalinehydrosulphite solution, blue-violet vats from which dyeings of similarshades are obtained on cotton. After being washed and exposed to theair, the color changes to extremely fast orange or orange-red shades.

We have also found that the properties of the halogeniferous vatdyestuffs can be substantially improved by introducing several differenthalogens into the allo-ms-naphthodianthrones or msanthradianthrones.This is effected by treating the said anthrone derivatives withdifferent halogens either concurrently or successively, for example withchlorine and bromine, or suitable agents which liberate halogens. andpreferably in presence of solvents or diluents and in pres-' ence orabsence of halogen-transferrers. The introduction of different halogensinto the allo-ms-naphthodianthrones or ms-anthrad'ianthrones may also beeffected by introducing into such halogen-allo-ms naphthodianthrones orhalogen-ms-anthradianthrones 7 tion.

which are still capable of taking up more halogen, another halogen,which differs from that already contained in the original sub stance,thesaid introduction being carried out in the manner already described.This process furnishes excellent yields. The resulting dyestuffs givebrilliant scarlet to red dyeings on cotton from a blue-violet vat.

For example the dichlor-dibrom-allo-ms- 'naphthodianthrone prepared bythis process dyes cotton a considerably faster and deeper red thanfisobtained from tetrabrom-allo ms-naphthodianthrone. Apart from thevaluable shade, the resulting dyestuffs also dis play, in many cases,surprisingly improved properties as regards fastness.

The following examples will further explainthe nature of the inventionwhich however is not restricted to these examples. The parts are byweight.

Example 1 dissolves to a green solution in concentrated sulfuric acidand gives violet dyeings on cottonfrom a vat of the same color, thecolor changing to orange after exposure to the air and washing.

Example 2 10 parts of 2.2-dimethyl-ms-benzdianthrone are stirred at 110to 120 G. into a meltof parts of caustic potash and parts of ethylalcohol, the mixture being then heated to 170 to 175 C. for 6 hours orthereabouts. The reaction mass is treated with hot water, and thedyestuif is precipitated by means of an air blast and filtered bysuction. It is identical with the product described in Example 1.

Example 3 1 part of 2.2-diinethyl-ms-benzdianthrone is dissolved in 40parts of aniline and after addition of 8 parts of powdered causticpotash, is boiled for about 1 hours. The aniline is then driven off bysteam distillation and the residue is filtered by suction. The resultingdyestuff behaves 1n the same way as that produced in Example 1.

Example 4 1 part of -l.4-dichlor-2.Q-dimethylmsbenzdianthrone is stirredand boiled in 20 parts of nitrobenzene and 8 parts of potassiumcarbonate, or calcined sodium carbon ate,

for 1 hours, and is then treated as in Example 1. The new dyestufl is abrown powder which dissolves to a greenish blue solution in concentratedsulfuric acid. It gives brown dyeings on cotton from a violet vat.

Example 5 2.2-'limethyl-ms-benzdianthrone is introduced at 210 G. into atenfold amount of fused caustic potash. After stirring for about twohours and dissolving the mass in water, the dyestulf is precipitated byan air blast and filtered by suction. The dyestuff is identical withthat described in Example 1.

E xample 6 1 part of the pro-duct obtainable according to Example 1 isthoroughly triliurated with 20 parts of aluminium chlorid, and heated at150 to 155 C. for 1. hours and, after the addition of ice and dilutehydrochloric acid, is filtered by suction. The resulting dark brownpowder may be purified by boiling it with dilute hypochlorite solution.It forms a light brown powder, which may be crystallized in small brownneedles from nitroben- Zene. The color of the solution in concentratedsulfuric acid is violet. trong golden-yellow dycings are obtained oncotton from a blue violet vat.

E xample '7 1 part of the initial substance referred to in Example 6 isdissolved in 25 parts of trichlorbenzene and 10 parts of powderedaluminiuin chlorid are stirred in at from 140 to 145 C. After stirringfor about 1% hours, ice and oilute hydrochloric acid are added, and thesolvent is expelled with steam. The resulting product is identical withthe prod not obtained in Example 6.

E xample 8 1 part of the condensation product obtainablefroni 1.1-dichlor-22-dimethyl-ms-bena dianthrone, according to Example 4-, ismixed with 20 parts of aluminium chlorid and heated to from 145 to 150C. for 1 hours. The mass is treated as in Example 6. The resulting brownpowder, dissolves to a violet solution in concentrated sulfuric acid,and gives yellow dyeings on cotton from a violet vat.

Example 9 The manganese dioxid may be replaced by lead dioxid,saltpetre, lead tetra-acetate or similar oxidizing agents.

Example E mample 1.1

18 1 part of 2.2-dimethyl-nis-naphthodianthrone is introduced at 110 to120 G. into a melt of 5 parts of caustic potash and 5 parts of ethylalcohol. The temperature is raised to from 170 to 175 C. and maintainedat flthat temperature for another 6 hours, the melt being then dissolvedin Water. After the resulting dyestuff has been precipitated by an airblast, it is filtered by suction; the brown reaction product may bepurified by 28 treatment with hypochlorite solution. The dyestuffdissolves in concentrated sulfuric acid to a violet solution, and givesgoldenyellow dyeings, fast to light and chlorine, on cotton from ablue-violet vat. It is proba- 30 bly identical with the productdescribed in Example 0.

Example 19 1 part of 2.2-dimethyl-ms-naphthodian- 36 throne isintroduced at 210 G. into a melt of 10 parts of caustic potash, andafter being kept at from220 C. to 230 C. for a further two hours, themass is treated as in Example 11. The resulting dyestutt is identical 40with that obtainable according to that example.

Example 15 1 part of 4.4-dichlor-2.2-dimethyl-msnaphthodianthrone isstirred and boiled in 10 parts of nitrobenzene, with addition of 10parts of potassium carbonate, for about 4 hours, then filtered bysuction after cooling, the resulting dyestuff being freed from thepotassium carbonate by boiling with water. The product is abrownish-yellow powder, which dissolves to a violet solution inconcentrated sulfuric acid and gives orange-yellow dyeings on cottonfrom a brown-violet 55 vat.

E'zmmple 1.4

2.2'-dimethyl ms naphthodianthrone is stirred and boiled in 10 parts ofnitrobenzene, 6 with addition of 4 parts of barium oxid, for about 4hours. After filtration by suction, the resultin dyestuif is freed fromadmixed barium oxi by boiling with dilute hydrochloric acid; it isidentical with the product obtained in Example 11.

Example 15 1 part of the vat dyestuif obtainable according to Example 1is dissolved in 10 to 12 parts of nitrobenzene, whereupon 0.1 part ofiodine is added and 1% parts of sulfuryl chlorid are stirred in, drop bydro at 60 C. Stirring is continued for a urther 6 hours whereupon themass is allowed to cool and the dichlor-allo-ms-naphthodianthroneseparated in crystalline form is filtered off by suction. It dissolvesto a green solution in concentrated sulfuric acid, and can be recovered,therefrom, as an orange paste, by precipitation with water. It givesorange dyeings on cotton from a violet vat.

Example 16 A current of dry chlorine is passed for an hour through aboiling solution of the product described in Example 1 in 10 parts oftrichlorbenzene to which 0.1 part of iodine has been added. The solventis then expelled with steam, and the residue is preferabl dissolved inconcentrated sulfuric acid an precipitated therefrom by dilution. Theresulting product has the same properties as that obtained in Example15.

E (ramp le 1'7 1 part of the product described in Example 1 is dissolvedin 10 parts of nitrobenzene, whereupon 1 part of bromine is added andthe mixture gradually heated, while stirring, to 150 C. After stirringfor 4 hours at this temperature, the mixture is allowed to cool, and thedeposited brownish-red crystals are filtered by suction. The resultingdyestuff which is a dibrom-allo-ms-naphthodianthrone may berecrystallized from nitrobenzene and then forms brick-red needles, whichdissolve to an emerald green solution in concentrated sulfuric acid.Very strong and clear scarlet dyeings are obtained on cotton from aviolet vat.

Ewample 18 1 part of the product obtainable according to Example 4 isdissolved in 10 to 12 parts of nitrobenzene, 3 parts of bromine beingthen stirred in, drop by drop, at 160 (1., this temperature beingmaintained for 4 hours and the dyestufi' filtered by suction when cold.It gives violet red dyeings on cotton from a violet vat.

Earample 1!) 1 part of the original substance used in Example 17 isdissolved in 10 parts of nitrobenzene, 0.05 part of iron filings beingthen added. The temperature is raised to 160 C. and 2 parts of bromineare added by drops. After stirring for 4 hours at the same temperature,the mixture is treated as in Example 17. The resulting dyestuff which isa tetrabroin-allo-ms-naphthodianthrone gives brilliant red dyeings oncotton from a violet vat.

Emam-ple 20 E wamp le 21 parts of ms-anthradiantln-one are dissolved in250 to 300 parts of nitrobenzene, and after addition of 0.5 part of ironfilings or powder are treated with about parts of bromine, stirred in at160 C. Stirring is continued for about lhours at the same temperature,and the dyestuff is filtered by suction after cooling. According toanalysis, it is a dibromine derivative. It gives a violet solution inconcentrated sulfuric acid, and a bluish-violet vat which furnishesorange dyeings on cotton.

Example 22 A suspension of 1 part of ins-anthradianthrone in parts ofphosphorus oxychloride is boiled for 1 to 2 hours with 10 parts ofphosphorus pentachloride, after which the reaction product is decomposedwith water and filtered off by suction. The resulting brownmonochlor-Ins-anthradianthrone may be purified with hypochlorite; itgives ex tremely fast orange dyeings on cotton from a bluish-violet vat.

E sample 5 analysis, the resulting brown powder is adibrome-ms-anthradianthrone; it can be purified by treatment withhypochlorite or by crystallization from nitrobenzene. It furnishesstrong orange-red dyeings on cotton from a bluish-violet vat.

Example 24 1 part of the dyestuif described in Example 1(allo-ms-naphthodianthrone) is heated with 3 parts of bromine to 100 C.for about 12 hours under pressure. The reaction product is dissolved indilute caustic soda solution and filtered by suction. It consists of abrown powder, which dissolves to a greenish-blue solution inconcentrated sulfuric acid, and gives strong orange-red dyeings oncotton from a bluish-violet vat.

Example 10 parts of the dyestuif obtainable accord- .ing to Example 1are dissolved in 100 parts of chlorsulfonic acid, whereupon 3 parts ofsulfur are added while stirring, followed by i parts of bromine. Themass is then heated to 65 to 70 C. and stirred at this temperature for 4hours, whereupon it is diluted with parts of concentrated sulfuric acidand poured onto ice. The resulting dibrom-msanthradianthrone is filteredoff by suction. It dissolves with a blue coloration in concentratedsulfuric acid and dyes cotton from a bluish-violet vat orange shades ofexcellent fastness.

Example 26 10 parts of chlor-allo-ms-naphthodianthrone (the dyestufi' ofExample 15) are dissolved in 100 parts of nitrobenzene and afteraddition of 1 part of iron filings are stirred with 10 parts of bromineat 160 0., the stirring being continued at the same temperature untilthe evolution of hydrogen bromide ceases in about 6 to 8 hours. Thedyestulf, which is filtered after cooling, and according to analysis isa dichlor-dibrom derivative, forms a. brown-red powder which dissolvesto a green solution in concentrated sulfuric acid. Brilliant red dyeingsare obtained from a bluish-violet vat.

E azample .27

10 parts of sulfuryl chlorid are stirred, drop by drop, at about G. intoa solution of 10 parts of allo-ms-napthodianthrone (obtainable inaccordance with Example 1) in 100 parts of nitrobenzene, 0.5 part ofiodine having been previously added. Stirring is continued, at the sametemperature, for further 6 hours, after which the temperature is raisedto 160 C. and 0.5 part of iron filings or powder is added, followed by10 parts of bromine. As soon as the evolution of halogen hydride hasceased, the treatment is con tinued as in Example 25, and the reactionproduct behaves in the same manner as that obtained in the said example.

E eeample 28 10 parts of ms-naphthodianthrone are suspended in 200 partsof trichlorbenzene, and chlorine is passed in for 2 hours at atemperature of 100 C. after addition of 0.5 part of sodium. The mixtureis allowed to cool and the reaction product is filtered by suction. 7After recrystallization from nitrobenzene pale yellow needles .are.obtained which dissolve in concentrated sulfuric aci' to a red solutionhaving about the color of fuchsine and showing a strong fluorescence.

Example 29 E sample 30 A mixture of 20 parts oftribrom-ms-benzdianthrone and 200 parts of aluminium chlorid is heatedto 160 to 165 C. until a sample of the reaction mixture dissolves inconcentrated sulfuric acid to a red solution having about the color offuchsine. This will be the case in about 1 to 2 hours. The reactionmixture is then decomposed with dilute hydrochloric acid and thetribrom-msnaphthodianthrone formed is filtered by suction. Vhenrecrystallized from nit-robenzene it forms pale yellow needles.

Example 31 10 parts of trichlor-ms-l:ienzdianthrone are dissolved in 600parts of concentrated sulfuric acid and manganese dioxid is added untilthe initially blue solution has turned to a red having about the colorof fuchsine. The reaction mixture is poured onto ice and thetrichlor-nis-naphthodianthronc formed is filtered by suction.

W'hat we claim is:

1. As new articles of manufacture, vat dyestuffs which are considered tocontain the system in which dyestufis two anthrone radicals are solinked together as to form two more hexar gon rings.

2. As new articles of manufacture, vat dyein which two anthrone radicalsare linked by one hexagon ring to the action of alkaline agents.

4. The process of producing new vat dyestufis which consists insubjecting a 2.2'-dimethyl-ms-benzdianthrone to the action of alkalineagents.

The process of producing new vat dyestuffs which consists in subjectinga 2.2- dimethyl-msbenzdianthrone to the action of an alkaline condensingagent.

6. The process of producing new "at dyestufl's which I consists insubjecting a 2.2 dimethyl-ms-benzdianthrone to the action of an alkalinecondensing agent in an inert organic diluting medium.

7. As new articles of manufacture, vat dyestuffs which are considered tocontain the system our hands.

MAX ALBERT KUNZ. KARL KoBERLE.

